Organotin miticidal and insecticidal compounds

ABSTRACT

A composition of matter is described herein which has insecticidal and mitricidal activity and methods of use. The composition may be defined by the following generic formula ##STR1## wherein X can be oxygen or sulfur; R 1  and R 2  can be the same or different and can be selected from lower alkyl, lower alkoxy, cycloalkoxy, thiophenyl, haloalkyl, alkoxythioalkyl, thiocyano, furfuryloxy, alkyldioxolanealkoxy and sulfolaneyloxy.

This is a division, of application Ser. No. 644,703, filed Dec. 29,1975, now U.S. Pat. No. 4,012,421 which is a division of applicationSer. No. 482,033, filed June 24, 1974, which in turn is a division ofapplication Ser. No. 293,974, filed Oct. 2, 1972, now abandoned, whichin turn is a continuation-in-part of application Ser. No. 208,046, filedDec. 10, 1971, now abandoned.

BACKGROUND OF THE INVENTION

Among the many insecticidal and miticidal compounds available, theorganotin compounds have reached a relatively high degree of commercialsuccess. Specifically, the organotins described in U.S. Pat. No.3,264,177, 3,591,614 and 3,591,615 are widely used. These compounds,however, suffer from considerable unstability due to the presence of anester linkage to the tin atom. Thus, these compounds are quitesusceptible to hydrolysis on use. Additionally, the organotin compoundsdescribed in U.S. Pats. No. 3,321,361 and 3,321,365 are useful asinsecticides. However, these compounds are quite toxic to vegetation andthus have extremely limited use.

BRIEF DESCRIPTION OF THE INVENTION

It has been discovered that certain organotin compounds have relativelylow phytotoxicity properties and are relatively stable. These organotincompounds may be defined by the following generic formula ##STR2##wherein X can be oxygen or sulfur; R₁ and R₂ can be the same ordifferent and can be selected from a group consisting of lower alkyl,lower alkoxy, cycloalkoxy, thiophenyl, haloalkyl, alkoxythioalkyl,thiocyano, furfuryloxy, alkyldioxolanealkoxy and sulfolaneyloxy. Theterm alkyl is defined as branched or straight chain alkyls having from 1to about 6 carbon atoms.

DETAILED DESCRIPTION OF THE INVENTION

In the practice of the present invention, the compounds of the presentinvention are manufactured by reacting an alkyl tin halide with analkali phosphate in a neutral solvent. The halide moiety in the alkyltin halides can be selected from a group consisting of chlorine, bromineand iodine. After the compounds of the present invention are formed,they can be applied to the habitat in an effective amount to controlrespective mites and insects.

The following examples illustrate the merits of the present invention:EXAMPLE 1 ##STR3##

A mixture was formed containing 10.1 grams of tricyclohexyltin chloride(0.025 M), 7.6 grams potassium diisopropyl dithiophosphate (0.03 M) and100 ml. of acetone. The mixture was heated to reflux for 1.5 hours andthen filtered. The filtrate was evaporated in vacuo and taken up inwater (100 ml.) and methylene chloride (100 ml.), dried over magnesiumsulfate and evaporated in a vacuum to yield 6.5 grams of product.

EXAMPLE 2 ##STR4##

The procedure of Example 1 was repeated in its entirety except 8.4 gramsof potassium diisobutyl dithiophosphate was substituted for thepotassium diisopropyl dithiophosphate.

Other compounds were made in a similar manner using appropriate startingmaterials. The compounds are listed in Table I.

                                      TABLE I                                     __________________________________________________________________________    Example 3                                                                             ##STR5##                                                              Example 4                                                                             ##STR6##                                                              Example 5                                                                             ##STR7##                                                              Example 6                                                                             ##STR8##                                                              Example 7                                                                             ##STR9##                                                              Example 8                                                                             ##STR10##                                                             Example 9                                                                             ##STR11##                                                             Example 10                                                                            ##STR12##                                                             Example 11                                                                            ##STR13##                                                             Example 12                                                                            ##STR14##                                                             Example 13                                                                            ##STR15##                                                             Example 14                                                                            ##STR16##                                                             Example 15                                                                            ##STR17##                                                             Example 16                                                                            ##STR18##                                                             __________________________________________________________________________

insecticidal Evaluation Tests

The following insect species are subjected to evaluation tests forinsecticidal activity.

1. Housefly (HF) -- Musca domestica (Linn.)

2. Lygus Bug (LB) -- Lygus hesperus (Knight)

3. Bean Aphid (BA) -- Aphis fabae (Scop.)

4. Two-spotted Mite (2-SM) -- Tetranychus urticae (Koch)

5. Salt-Marsh Caterpillar (SMC) -- Estigmene acrea (Drury)

6. Beet armyworm (BAW) -- Spodoptera exigua (Hubner)

7. Tobacco budworm (TBW) -- Heliothis virescens (Fabricius)

Aliquots of the toxicants, dissolved in an appropriate solvent, arediluted in water containing 0.002% of a wetting agent, Sponto 221® (apolyoxyether of alkylated phenols blended with organic sulfonates). Testconcentrations range from 0.1% downward to that at which 50% mortalityis obtained. In the tests, for these species, ten 1-month old nymphs ofthe Lygus Bug are placed in a circular cardboard cage sealed on one endwith cellophane and covered by a cloth netting on the other. Testconcentrations for the Lygus Bug ranged from 0.05% downward to that atwhich 50% mortality was obtained. Each of the aqueous suspensions of thecandidate compounds are sprayed onto the insects through the clothnetting by means of a hand spray gun. Per cent mortality in each case isrecorded after 72 hours, and the LD₅₀ value expressed as per cent oftoxicant in the aqueous spray is recorded. The results are in Table IIunder Column LB.

The following procedure is used to test houseflies: A stock solutioncontaining 0.1 per cent by weight of the toxicant in an appropriatesolvent is prepared. Aliquots of this solution are combined with 1milliliter of an acetone-peanut oil solution in a glass Petri dish andallowed to dry. The aliquots are selected to achieve desired toxicantconcentration ranging from 100 μ per Petri dish to that at which 50%mortality was attained. The Petri dishes are placed in a circularcardboard cage, closed on the bottom with cellophane and covered on topwith cloth netting. Twenty-five female houseflies are introduced intothe cage and the per cent mortality is recorded after 48 hours. The LD₅₀values are expressed in terms of μ per 25 female flies. LD₅₀ valuesobtained in the above-mentioned housefly test are found in Table IIunder Column HF.

The compound is dissolved in the appropriate solvent and diluted to aconcentration of 0.1 per cent with water containing 0.015% Sponto 221 ®.A portion of the leaf from a bitter dock (Rumex obtusifolius) plant isimmersed in the test solution for 10 seconds and allowed to dry. Whendry, the leaf is placed in a Petri dish containing a 9 cm disc ofmoistened filter paper. Five 3rd-instar saltmarsh caterpillar larvae areplaced on the treated leaf. Mortality is recorded after 72 hours. Testconcentrations range from 0.1 per cent to that at which 50% mortality isobtained. This latter concentration is recorded as the LD₅₀ value forthe test compound.

The test method for the cotton bollworm, beet armyworm and tobaccobudworm is identical to the above except that Romaine lettuce (Lactucasativa) is used as the test plant rather than bitter dock.

The compounds are also active against two-spotted mite (2-SM)Tetranychus urticae (Koch). Pinto bean plants (Phaseolus sp.) areutilized as the host plant and infested with 50 to 75 mites of variousages. Twenty-four hours after infestation, they are sprayed to the pointof run off with aqueous suspension of the toxicant. Test concentrationsrange from 0.05% to that at which 50% mortality is obtained. The valuesobtained in this test are found in Table II under the Columns 2SM-PE and2SM-Eggs. The compounds are also active against bean aphid (Aphis fabae(Scop.)) as a contact toxicant. The same test procedure as given for thetwo-spotted mite above is used for the bean aphid except nasturtium(Tropaeolum sp.) plants approximately 2 to 3 inches tall are used as thehost plant. The LD₅₀ values obtained for the compounds of this inventionare found in Table II under Column BA.

The compounds of this invention are generally embodied into a formsuitable for convenient application. For example, the compounds can beembodied into pesticidal composition which are provided in the form ofemulsions, suspensions, solutions, dusts and aerosol sprays. In general,such compositions will contain, in addition to the active compound, theadjuvants which are found normally in pesticide preparations. In thesecompositions, the active compounds of this invention can be employed asthe sole pesticide component or they can be used in admixture with othercompounds having similar utility. The pesticide compositions of thisinvention can contain, as adjuvants, organic solvents, such as sesameoil, xylene range solvents, heavy petroleum, etc.; water; emulsifyingagents; surface active agents; talc; pyrophyllite; diatomite; gypsum;clays; propellants, such as dichlorodifluoromethane, etc. If desired,however, the active compounds can be applied directly to feedstuffs,seeds, etc. upon which the pests feed. When applied in such a manner, itwill be advantageous

                                      TABLE II                                    __________________________________________________________________________               2 SM                                                                    HF    LB   BA   PE     EGGS   SMC   BAW   TBW                            Example                                                                            μg/25 ♂                                                                     %    %    %      %      %     %     %                              __________________________________________________________________________    1    >100  >.05 .008 0.0008 0.03   0.03  0.01  >.1                            2    100   >.05 .03  0.0008 0.003  0.03  0.03  0.08                           3    80    .05  .01  0.0005 0.003  0.1   0.05  0.1                            4    80    .05  .03  0.0008 0.003  >.1   0.03  >.1                            5    85    .05  .03  0.001  0.008  0.05  0.01  >.1                            6    50    >.05 .01  0.001  0.003  0.01  0.03  >.1                            7    50    >.05 .03  0.003  0.008  0.008 0.008 0.1                            8    90    >.05 .05  0.0005 0.003  --    0.01  0.1                            9    100   >.05 >.05 0.0003 0.008  >10   --    >.1                            10   80    >.05 .03  0.0005 0.008  .1    .01   .01                            11   65    >.05 >.05 0.0003 0.003  .1    .01   >.1                            12   65    >.05 .03  0.0003 0.003  .1    .01   >.1                            13   65    >.05 .03  0.0003 0.003  .1    .03   >.1                            14   65    >.05 .05  0.0003 0.003  >.1   --    >.1                            15   65    >.05 .03  0.0008 0.003  >.1   .05   >.1                            16   65    >.05 .01  0.0003 0.0008 0.03  <0.005                                                                              .008                           __________________________________________________________________________     to use a compound which is not volatile. In connection with the activity     of the presently disclosed pesticidal compounds, it should be fully     understood that it is not necessary that they be active as such. The     purposes of this invention will be fully served if the compound is     rendered active by external influences, such as light or by some     physiological action which occurs when the compound is ingested into the     body of the pest.

The precise manner in which the pesticidal compositions of thisinvention are used in any particular instance will be readily apparentto a person skilled in the art. Generally, the active pesticide compoundwill be embodied in the form of a liquid composition; for example, anemulsion, suspension, or aerosol spray. While the concentration of theactive pesticide in the present compositions can vary within rather widelimits, ordinarily the pesticide compound will comprise not more thanabout 15.0% by weight of the composition. Preferably, however, thepesticide compositions of this invention will be in the form ofsolutions or suspensions containing about 0.1 to 1.0% by weight of theactive pesticide compound.

what is claimed is:
 1. A compound of the formula ##STR19##